Photographic elements containing bleachable mordanted dye layers



1966 .J. JONES ETAL 3,Z32,fi

PHOTOGRAPHIC ELEMENTS CONTAINING BLEACHABLE MORDANTED DYE LAYERS Filed Jan. 22, 1962 LIGHT-SENSITIVE SILVER HALIDE EMULSION J eELATlhz CONTAINING POLY CL-METHYL ALLYL-N-GUANIDYLKETIMINE UN\\\\\\ AND 4-[Z-(3-ETHYL-2BHI-BENZ0 A20LYLIDENE)- 1,2 -ZBUTENYLIDENE]-3-METHYLI (P-SULFOPHENYL -2- PYRAZOLIN 5 ONE i 1 MONOSUL FONATED SUPPORT LIGHT-SENSITIVE SILVER HALIDE EMULSION GELATIN CONTAINING= (I) POLY(C 1:METHYL ALLYLN-GUANIDYLKETIMINE), (2) 4-[(3-ETHYL-2- (sH)- BENZOXAZ OLYL IDEN E) ETHYLIDENE]3-METHYL-I-(P-SULFOPHENYL) -Z-PYRAZOLIN'5-ONE, MOI-\IOSULFONATED, AND (a) Bl5(I-BUTYL-3-CARBOXYMETHYL HEXAHYDRO-Z,

4, 6-TRIOXO-5-PYRIMIDINQTEIMETH INOXONOL SUPPORT fl/lA LIGHT-SENSITIVE SILVER HALIDE EMULSION 1O 47 GELATIN CONTAININ6= 14% (I) POLY((l-METHYL ALLYL-N-GUANIDYLKETIMINE),

(2) 4-[(5-ETHYL2 (3H) -BENzo AZOLYLIDENE) 12 ETHYLlDENE]-5-METHYL-I-(p-SULFOPHENYL)- 2- PYRAZOLIN-5-ONE, MON-OSULFONATED, JET (3)BI5(l-BWYL-5-CARBOXYMETHYL HEXAHYDRO-Z,

4, 6-TRIOXO -5- PYRIMIDINE)TRIMETHINOXONOL, AND (4) BISD-(P-SULFOPHENYQ-BMETHYL2- PYRAZOLIN-E-ONE (4)] PENTAMETHINOXONOL SUPPORT Jean/E. Jenes Kiz'by/M. Milion/ INVENTORS ATTORNEY AGENT United States Patent 3,282,699 PHOTOGRAPHIC ELEMENTS CONTAINING BLEACHABLE MORDANTED DYE LAYERS Jean E. Jones and Kirby M. Milton, Rochester, N.Y., as-

signors to Eastman Kodak Company, Rochester, N.Y.,

a corporation of New Jersey Filed Jan. 22, 1962, Ser. No. 167,666 17 Claims. (Cl. 96---84) This invention relates to new bleachable mordanted dye layers and more particularly to photographic ,elements containing these layers as antihalation layers.

It is known that photographic elements require for many purposes to have light-screening substances incorporated therein. Such a light-screening substance may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such light-screening substance; or it may be in a layer not containing a light sensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example, to reduce halation).

In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, (b) in layers arranged between differentially color sensitized emulsions, e.g., to protect redand green-sensitive emulsions from the action of blue light, and (c) in backings forming the so-called antihalation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.

Bleachable dye layers are useful in photographic film elements as antihalation layers between the support and light-sensitive silver halide emulsion layers in order to give improved halation protection, to prevent light being transmitted through the film support to the emulsion from the edge of a roll of film element and in instances where it is desired to apply processing solutions to one surface of an element only and still obtain halation protection before processing and a clear element after processing. Bleachable dye layers are also useful in filter interlayers and in antihalation layers. In all of these applications, the dyes must be made nonwandering under the conditions encountered in the use and storage of films in order to prevent undesirable sensitometric effects. The color of the dye layer, furthermore, must be discharged on processing with no adverse eifects upon the development of the film. The dyes must, of course, absorb light in the desired region of the spectrum. In the past, some dyes have been made nonwandering by the use of various mordants, e.g., Silberstein et al. US. Patent 2,527,583, issued October 31, 1950. Previously known mordant-dye compositions, however, which are suificiently nonwandering to use in layers in contact with emulsion layers are bleached only with difliculty or not at all during normal processing of the film. Those known compositions of dyes and mordants which bleach more easily are not sulficiently nonwandering. The dye migrates to the light-sensitive layers with a consequent deleterious effect upon the sensitometric properties of the film.

It is, therefore, an object of our invention to provide a new class of bleachable mordanted dye layers in which the acid substituted benzoXazole-pyrazolone merocyanine dyes are made nonwandering with certain basic mordants.

Another object is to provide a dye-mordant combination which is nonwandering in the water-permeable hydrophilic "ice layers containing it so that the layer can be coated directly under light-sensitive silver halide emulsion layers and yet is a dye-mordant combination which is readily broken by contact with normal processing solutions so the dye is completely discharged from the layer.

Another object is to provide a photographic element comprising a support coated with a water-permeable hydrophilic colloid layer containing our dye-mordant combination, said layer being coated with a light-sensitive silver halide emulsion layer.

Still further objects will be evident from the following specification and claims.

These and other objects are accomplished according to our invention by using an antihalation layer comprising water-permeable hydrophilic colloid, a basic mordant and a dye having two acidic groups attached to it, that is, having the nucleus at one end of the molecule substituted with one sulfo, one sulfoalkyl, one sulfophenyl, one carboxy, or one carboxyalkyl group and the nucleus at the other end of the molecule substituted with one sulfo, one sulfoalkyl, one sulfophenyl, one carboxy or one carboxyalkyl group in any of the various combinations of these groups on a dye molecule, and having coated over said colloid layer a light-sensitive silver halide emulsion layer.

Included among the dyes that are advantageously used according to our invention are those having the formula:

wherein R represents an alkyl group such as methyl,-

ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkyl group, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or a sulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.; Z represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series (including benzoxazole and benzoxazole substituted with substitutions such as methyl, ethyl, phenyl, methoxy, ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazole series which has a sulfo-substituent on the benzene ring as well as one or more of the above-mentioned simple substituents, such that when R represents an alkyl group, Z represents the sulfo-substituted benzoxazole nucleus and when R represents a carboxyalkyl group or a sulfoalkyl group, Z represents the nonmetallic atoms necessary to complete a benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the sulfophenyl pyrazolinone series and n is an integer from 1 to 3.

Alternatively, the antihalation layer containing our dyemordant combinations may be coated between two or more silver halide emulsion layers in a multilayer element or as a backing layer on the side of the support away from the light-sensitive layers.

Our filter layers may also contain certain other dyes or pigments which have suitable releasing properties in the photographic processing solutions. These other dyes or pigments are selected to give with the Formula I dyes, the desired light-absorbing properties. Typical represent ative dyes of Formula I include the following:

DYE NO. 1

4-[ (3-ethyl-2 3H) -benzoxazolylidene) ethylldene] 3-methyl-1- (p-sulfophenyl)-2-pyrazolin-5-one, monsuLtona-ted DYE NO. 2

o N l 4- [4- 3-ethyl-2'( 3H -benzoxazolylidene) -2-burtenylidene] -3- methyl-l-(p sulfophenyl) 2-pyrazo1in-5-one, monosulfonated DYE NO. 3

41-[ (3-fi-carboxyethyl-2 (3H -benzoxaz0lylidene) ethylidene] -3- methyl-lp-sulfophenyl) 2-pyrazolin-5-one DYE NO. 4

l C 3 CH2CH2C 4-[4-(3-,H-ethy1-2 (3H)-benzoxazolylidene)=2-buteny1idene1-3- 'methyl-lp-sulfophenyl) -2-pyrazolin-5-one Dyes which are used to advantage in our light-filtering layers with dyes of Formula I include the oxonol dyes of the formula:

(II) ,-Q.- ,-Q,-\

o=o' brr-o11(=on-o11 1=-b=0 wherein Q and n are as defined previously, and the oxonol dyes of formula:

(III) -w- -W bis 1- (p-sulfophenyl) -3-methyl-2-pyrazolin-5-one- (4) methinoxonol,

bis[ 1- (p-sulfophenyl) -3 -methyl-2-pyrazolin-5-one- (4) tnimethinoxonol,

bis[ 1- (p-sulfophenyl -3-methyl-2-pyrazolin-5-one- (4) pentamethinoxonol, etc.

Typical examples of dyes having Formula III include dyes such as v I bis(l-butyl-3-carboxymethyl hexahydro-Z,4,6-tri0X0-5- pyrimidine) -trimethinoxonol, bis(1-butyl-3-carboxymethyl hexahydro-ZA,6-trioX0-5- pyrimidine) -pentamethinoxonol.

Typical inorganic pigments useful in our filter layers include materials such as lead chromate, Prussian blue, etc.

Particularly efiicacious combinations of our mordanted dyes include one or more dyes of Formula I with one or more dyes of Formula-III in addition to or in place of one or more dyes of Formula II.

The light-screening layers of our invention are prepared by coating on the photographic element or on its support, by methods well known in the art, a Water solution of the dye, a hydrophilic colloid binder and a coating aid such as saponin. In addition to these materials, it is advantageous to add a basic mordant to this solution to render the acid dye nonwandering. For most purposes, it is desirable to :add agents to harden the colloidal binder material so that the light-screening layer will remain intact in the photographic element during and following the processingoperation. The pH of the coating solution is adjusted when necessary by the usual methods to a level that is compatible with the light-sensitive emulsion layer.

In addition to the solubilized merocyanine dyes of Formula I, we have found that it is advantageous to use a new class of solubil ized dyes of the type of Formula I in which a 1,3-trimethylene bridge, such as a neopentylene group, is attached to the intercyclic polymethine chain of the dye molecule (in'which case n can have a value of 3 or 4 These dyes include the dyes such as described by Brooker and Heseltine U.S. Patent 2,856,404, issued October 14, 1958, but which have been substituted with an acidic radical as identified above. Representative dyes of this type include dyes, such as Dyes of this type can be prepared by condensing a N-sulfoalkyl heterocyclic quaternary salt containing a reactive methyl group with an intermediate of Formula I of U.S. 2,856,404.

Still other solubilized dyes of Formula I include those substituted with sulfoalkyl groups, such as 3-methyl-4-{[3- (4-sulfobutyl) -2 3H -benzoxazolylidene] ethylidene}-l-p-su1fophenyl-Z-pyrazolin-S -one, 3-methyl-4-[ (3-fii-Slllf06tl1Yl-2 3H) -benzoxazolylidene) ethylidene] l-p-sulfophenyl-2-pyrazolin-5-one, etc.

The proportions of dye, Water-permeable hydrophilic colloid binder, mord-ant, hardener, and coating aid used in making our light-screening layers may be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The method used to determine the optimum composition is Well known in the art and need not be described here.

The light sensitive layer or layers and the light-screening layer or layers of the photographic element may be coated on any suitable support material used in photogr-a-phy such as cellulose nitrate, cellulose acetate, synthetic resin, paper, etc.

Hydrophilie colloidal materials used as binders include gelatin, collodion, gum arabic, cellulose ester derivatives such as alkyl esters of carboXylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued August 1 6, 1960, polyvinyl alcohol, and others well known in the art. The above-mentioned arnphoteric copolymers are made by polymerizing the monomer having the formula:

oH2=oR COOH wherein R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general formula:

erized with a third unsaturated monomer in an amount of to 20 percent of the total monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers. The third monomer may contain neither a basic group nor an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allyl amine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; etc.

Our dyes are generally added to the water-permeable colloidal binder in water solution. In some instances, it may be advantageous to form an alkali metal salt of the dye by dissolving the dye in a dilute aqueous alkali metal carbonate solution, for example. Usually a coating aid, such as saponin, is added to the dyed colloidal suspension before coating it as a layer on the photographic element. The dyes are advantageously mordanted with a suitable basic mordant added to the colloidal suspension before coating.

Basic mordants that may be used include the basic mordants described by Minsk in U.S. 2,882,156, issued April 14, 1959, prepared by condensing a polyvinyl-0x0- compound such as a polyacrolein, a poly-'y-methylacrolein, a polyvinyl alkylene ketone, such as polyvinyl methyl ketone, polyvinyl ethyl ketone, polyvinyl propyl ketone, polyvinyl butyl ketone, etc., or certain copolymers containing acrolein, methacrolein, or said vinyl alkyl ketone components, for example, 1 to 1 molar ratio copolymers of these components with styrene or alkyl methacrylateswherein the alkyl group contains from 1 t0 4 Carbon atoms, such as methyl, ethyl, propyl, or butyl methacrylates in the proportions from about .25 to 5 parts by weight of the said polymeric oXo-compound with one part by weight of an aminoguanidine compound such as aminoguanidine bicarbonate, aminoguanidine acetate, aminoguanidine butyrate, etc.

One of the derived resin mordants described above is a guanidyl hydrazone derivative, that is, a derived polymer containing from 30 percent to 90 percent by weight of the recurring unit having the indicated structure:

wherein n represents 0 to 1, R represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms and X represents the anion of any suitable water-soluble monobasic inorganic acid such as hydrochloric acid or any water-soluble monobasic organic acid such as lactic acid, glycolic acid, alkanesulfonic acid containing from 1 to 4 carbon atoms such as methanesulfonic acid, n-butanesulfonic acid, etc., or of a water-soluble monobasic saturated aliphatic carboxylic acid containing from 2 to 4 carbon atoms such as acetic, propionic or butyric acids, the remaining 70 to percent of the resin molecule being unreacted vinyl oxo-compound, for example, acrolein, 7- methyl acrolein or vinyl alkyl ketone or combinations of these with styrene or an alkyl methacrylate in the proportions of from about 10 to percent by weight of the unreacted vinyl oxo-compound to form about 90 to 85 percent by weight of the styrene or alkyl methacrylate, where the starting copolymer contains these components in about a 1:1 molar ratio. The derived resins are ordinarily employed in the form of their soluble acid salts, preferably as the acetate salts, in which case the derived polymers preferably contain from about 50 to 85 percent by weight of the salt unit represented by the above general structural formula, the remainder of the resin molecule being composed of the said unreacted vinyl oxo-compound units.

Although it is possible to use other basic mordants known in the art, the preferred mordants are those described above. Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5,6-tetra-carboxy1ic dianhydride or adicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll, U.S. Patents 2,725,294 and 2,725,295, both issued November 29, 1955; a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers, U.S. Patent 2,725,304, issued November 29, 1955; a hisester of methane-sulfonic acid such as 1,2-di(metha.nesulfonoxy)-ethane as described in Allen and Laakso, U.S. Patent 2,726,162, issued December 6, 1955; 1,3-dihydroxymethylbenZimidazol-Z-one as described in July, Knott and Pollak, U.S. Patent 2,732,316, issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2 to 3 carbon atoms, such as B-methyl 'glutaraldehyde bis-sodium bisulfite as described in Allen and Burness, U.S. patent application Serial No. 556,031, filed December 29, 1955, now abandoned; a bis-aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster U.S. Patent 2,950,197, issued August 23, 1960; or 2,3-dihydroxydioxane as described in JefI'reys, U.S. Patent 2,870,013, issued January 20, 1959.

The photographic elements utilizing our light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any light-sensitive silver halide emulsion layers may be used in these photographic elements. The silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.

Our invention is further illustrated by the following examples describing the preparation of photographic elements containing our light-screening or antihalation layers.

Example I An aqueous solution was made containing 4.54 grams gelatin, 0.91 gram poly(u-methyl allyl-N-guanidylketimine), .153 gram saponin and 0.302 gram of Dye No. 1, a blue absorber, in a total weight of grams at a pH of 6.1. This solution was coated on a clear cellulose acetate film support at 4.6 grams/ft. and was then overcoated .with a fine-grained chlorobromide emulsion with panchromatic sensitization at a silver coverage of 257 mg. silver/ ft. A control containing no dye was coated on a clair support.

The film samples were developed for 6 minutes in a developer having the following composition:

DEVELOPER 1 Grams p-Methylaminophenol sulfate 2.2 Hydroquinone 8.8 Sodium sulfite (anhydrous) 72.0 Sodium carbonate (anhydrous) 48.0 Potassium bromide 4.0

Water to 1.0 liter.

The. developed film samples were then fixed for 10 minutes in a fixing bath having the following composi- Water to 1.0 liter.

7 Halation latitudes were obtained for each film sample using filtered and unfiltered light. The halation latitude values listed below represent the increase over normal required in log E exposure to give a halation density of 0.1 in the center of an 0.008 inch wide unexposed line.

It can be seen that a marked improvement in halation protection resulted from the use of our antihalation layer. After processing, no residual dye stain from the dye overcoat remained.

Example 2 An aqueous solution was made containing 4.54 grams gelatin, 1.34 grams poly (oz-methyl allyl-N-guanidylketimine), 0.27 gram saponin, 0.1165 gram Dye No. 1, 0.0495 gram bis(1-butyl-3-carboxymethyl hexahydro-Z, 4,6, trioxopyrimidine)trimethinoxonol, 0.1360 gram Dye No. 2, 0.0827 gram bis(1-butyl-3-carboxymethyl hexahydro-2,4,6-trioxo-5-pyrimidine)pentamethinoxonol, and 0.0518 gram of bis[1-(p-sulfophenyl)-3 -methyl-2- pyrazolin-5-one-(4) l-pentamethinoxonol in a total weight of 135.5 grams at a pH of 6.4. This resulting coating was overcoated with a fine-grained silver bromoiodide emulsion with a panchromatic sensitization at a silver coveFage of 260 mg. silver/fe A control was coated on gray-dyed cellulose acetate support. The films were exposed on an intensity scale sensitometer to a Daylight Type III source for of a second, clear and through a blue, a green and a red Wratten Filter Nos. 47, 58 and 25, respectively; developed for 5 minutes in a developer having the following composition:

The slight decrease in speed found was due to the considerably improved halation protection as shown by the following results, expressed as halation latitude to exposing light.

TABLE III Dye in Antihalation Layer Clear Blue Green Red No dye 1.65 1. 69 1. 78 1. 82 With antihalation dyes 2. 53 2. 91 3.16 2. 08

The dyes were thus mordanted sufficiently to prevent migration to an emulsion coated on the dye layer as shown by a lack of a sensitometric effect. Yet the dyes were discharged upon processing.

Example 3 An aqueous solution was made up as in Example 1 but which contained 4.54 grams gelatin, 0.588 gram poly(a-methyl allyl-N-guanidylketimine), 0.29 gram saponin, 0.907 gram lead chromate with an adsorption maximum at 410 III/L, 0.0985 gram Dye 2 and 0.0972 gram bis[l-(p-sulfoplienyl)-3-methyl-2-pyrazolin-5 one (4)] pentamethoxonol. This solution was coated as in Example l and overcoated with panchromatically sensitized silver bromoiodide emulsion of negative speed at a silver coverage of 588 mg. silver/ft? A control was coated on gray-dyed cellulose acetate support. The films were exposed as in the previous example and processed 9 minutes in the following composition,

DEVELOPER 3 Grams P-Methylaminophenol sulfate 1.5 Hydroquinone 1.3 Sodium sulfite (desiccated) 75.0 Sodium tetrabora-te-10H O 4.5 Potassium bromide .4

Water to 1.0 liter.

and fixed for 10 minutes in a fixing solution of Example 1 and washed. No dye stain remained in the processed element which had the antihalation dyes. The relative speed values and halation latitudes were determined and are tabulated below.

TABLE IV R1 Dye in Antihalation Layer eative Speeds Gamma Fog lIalation Latltude Clear Blue Green Red Clear Blue Green Red No dye 100 100 1 W... .3 9. 3.: .23 .3; a s 2.2% $3 DEVELOPER 2 Exam le 4 Water 500-0 An aqueous control solution was prepared which con- P-M l l sulfate tained 4.54 grams gelatin, 0.29 gram saponin, 0.1165 sodiumsulfite (deslccated) gram Dye 1, 0.0972 gram bis(1-butyl-3-carboxymethyl Hydroquinone hexahydro-2,4,6 trioxo 5 pyrimidine) trimethinoxonol S IlI metabofifie 2 and 0.641 gram of the mordant poly(a-methyl allyl-N- Potassium bromldc guanidylketimine) to a total weight of 135.5 grams at a Water to make 1. fi pH of 6.6. Another aqueous solution was prepared and fixed for 10 minutes in the fixing bath of Example 1. No residual dye stain remained in the antihalation layer. The relative speed values were determined for each film element, corrected to the control with a speed of 100 for both. clear and filtered exposures. The following results were obtained.

which diifered only in that the above mordant was replaced by an identical amount of polyvinylpyridinium metho-ptoluenesulfonate. The solutions were then coated on separate clear cellulose acetate supports to yield 5.22 grams of solution per square foot and dried. The resultant coatings were then overcoated With a coarse- 'except that it lacked one sulfonic acid group.

grained silver iodobromide emulsion at a coverage to yield 10 mg. of silver/ft.2. The two film samples were then exposed on an intensity scale sensitometer to a Daylight Type III source for of a second clear, developed for 7 minutes in a solution having the following composition,

DEVELOPER 4 Grams p-Methylaminophenol sulfate 3.0 Sodium sulfite (desiccated) 45.0 Hydroquinone 12.0 Sodium carbonate (monohydrated) 80.0 Potassium bromide 2.0

Water to 1.0 liter.

and fixed for 10 minutes in the fixing bath used in Example l. The relative speed value, gamma and fog were determined for these film samples and are tabulated in the table below.

Each of the mordants in the mordant-dye combinations used in this example illustrate their good characteristics, however, it will be noted that the combination with poly (a-methylallyl-N-guanidylketimine) is especially good.

Example Two undercoat antihalation layers were prepared in a manner similar to that described for the control coating in Example 4. These coatings differed in that a single dye, Dye 1, was used in one coating and a single dye, 4 [3-ethyl-2(3H)-benzoxazolylidene)ethylidene]-3-methyl-l-(p-sulfophenyl)-2-pyrazolin-5-one, was utilized in the other antihalation undercoating; and the mordant level was adjusted since only a single dye was used to maintain the previous mordant to dye ratio of 3:1. These layers as well as a clear cellulose acetate control were overcoated, exposed and processed as described in Example 1. The relative speed values obtained are tabulated below.

Antihalation layers were prepared and overcoated in a manner similar to those described in Example 5. The control coating contained Dye 2 in the undercoat while the other coating contained the dye 4-[4-(3-ethyl-2(3H)- benzoxazolylidene) 2 butylidene]-3-rnethyl-1-(p-sulfophenyl)-2-pyrazolin-5-one which was identical to Dye 2 These elements were exposed and processed as in Example 1. The relative speed values obtained are tabulated below.

Examples 5 and 6 illustrate that substantial speed losses resulted when the mordanted antihalation dyes contained onlyone acid group in the dye molecule. The addition of a second acid group increases the dye-mordant bond so that the dye does not wander into the emulsion overcoat and thereby exhibit an over-all loss in speed of the photographic element. When the preferred dye-mordant combinations were used, the only speed loss observed was due to improved protection from halation and is exhibited, therefore, only in the spectral region in which the dye absorbs.

Our invention is still further illustrated by the preparation or reference to preparation of typical dyes used in our light-filtering layers.

Dye No. 1 was prepared by dissolving 5 grams of 4- (3 ethyl-2 3H) -benzoxazolylidene ethylidene] -3-methyl-l-p-sulfopheny1-2-pyrazolin-S-one in a mixture of 10 ml. concentrated sulfuric acid, 15 cc. of 20 percent oleum and 0.1 gram ferric chloride, heating the mixture at an external flask temperature of 200-210 for 1 hour. After chilling, the mixture was poured onto 200 grams of ice.

The crude dye was collected on a filter and then twice recrystallized by dissolving in hot methanol as the triethylamine salt, filtering and precipitating the dye by the addition of concentrated hydrochloric acid. The yield of purified dye after two recrystallization's was 3.9 grams, M.P. 3l0 C.

Dye No. 2 was prepared in the same manner as Dye No. 1 but using 4-[4-(3-ethyl-2(3H)-benzoxazolylidene)- 2 butenylidene]-3-methyl-l-p-sulfophenyl-2-pyrazolin-5- one. The purified dye had a M.P. 300 C.

Dye No. 3 was prepared as follows.

2 B acetam'lidovinyl-3-[3-carboxyethylbenzoxazolium iodide (2.39 grams; 1 mol.) and 3-methyl-1-p-sulfophenyl 2-pyrazolin-5-one (1.27 grarn; 1 mol.) were suspended in pyridine (10 cc.) and triethylamine (0.51 gram; 1 mol.) was added. The mixture was heated under reflux for 5 minutes and after chilling, the crude dye Was precipitated with ether. The ether Was decanted and the residue stirred with methanolic HCl and chilled. The crude dye was collected on a filter and then twice recrystallized by dissolving in methanol by the addition of piperidine, filtering and acidifying the filtrate with methanolic HCI.

' The pure dye was obtained as light brown crystals in a 4 percent yield, M.P. 2889 dec.

Dye No. 4 was prepared by the method used for Dye No. 3 but using an equivalent amount of 2-(4 methoxybutadienyl)-3-/3-carboxymethylbenzoxazolium iodide in place of Z-B-acetanilidovinyl-3-B-carboxyethylbenzoxazoliu'm iodide.

The preparation of dyes of Formula II is illustrated by the following representative procedures.

Bis[l (p-sulfophenyl) 3-methyl-2-pyrazolin-S-one- (4)]-methinoxonol, for example, was prepared by condensing 1 (p-sulfophenyl)-3-methyl-2-pyrazolin-S-one with ethyl orthoformate in acetic anhydride by heating under reflux, then cooled and mixed with about cc. diethylether. The dyestulf was precipitated, washed with ether and dried.

The corresponding trimethinoxonol was prepared by a similar process in which 2 moles of 1-(p-sulfophenyl)3- methyl-Z-pyrazolin-S-one was condensed with B-anilinoacrolein-anil in methanol solution containing 3 moles of triethylamine.

The corresponding pentamethinoxonol dye was prepared by a similar process using glutacondialdehyde-dianilide in place of the anil. I

The preparation of dyes of Formula III is illustrated by the following representative preparations.

Bis(1 butyl 3-carboxymethylhexahydro-2,4,6-trioxo- S-pyrimidine)trimethinoxonol was prepared by heating under reflux for 5 minutes a mixture of 1-butyl-3-carboxymethyl'barbituric acid (1.2 gram), B-ethylacroleinacetal (0.9 gram) pyridine (2.5 cc.) and triethylamine (1.4 cc.). The reaction mixture was chilled, poured into water and acidified with concentrated HCl. The dye was collected by filtration and recrystallized from ethanol. It had an absorption maximum in ethanol at 493 mp" Bis(l-butyl-3-carboxymethylhexahydro 2,4,6 trioxo- 5-pyrimidine)pentamethinoxonol was prepared by heating a mixture of 1-butyl-3-carboxymethylbarbituric acid (3.6 grams), glutaconic aldehyde dianilide hydrochloride (2.13 grams), ethanol (30 cc.) and triethylamine (8.4 cc.) on a steam bath for minutes. The dye solution was chilled and acidified with concentrated HCl (12 cc.) and the solution was poured into water. The precipitated dye was collected, washed with water and dried. The product melted at 88 C. and had an absorption maximum in water at 590 mg.

The l-butyl-3-carboxymethylbarbituric acid used was prepared by reacting 1-butyl-3-ethoxycarbonylrnethylbarbituric acid with potassium hydroxide in methanol, then separating the potassium salt by filtration, washing with methanol, and acidifying an aqueous solution of the potassium salt with hydrochloric acid.

The accompanying drawing containing FIGS. 1, 2 and 3 still further illustrates our invention. FIGS. 1, 2 and 3 represent greatly enlarged cross-sectional views of lightsensitive photographic elements containing our light-absorbing water-permeable colloid layer.

' FIG. 1 shows support 12 coated with an antihalation layer 11 comprising gelatin, poly(a-methyl .allyl-N- guanidylketimine) and the dye 4-[4-(3-ethyl-2(3H)-benzoxazolylidene)-2-butenylidene]-3-methyl 1 (p sulfophenyl)-2-pyrazolin-5-one, monosulfonated, over which is coated light-sensitive silver halide emulsion layer 10.

FIG. 2 shows support 12 coated with antihalation layer 13 comprising gelatin, poly(u-methyl allyl-N-guanidylketimine) the dye 4- 3-ethyl-2 3H) -benzoxazolylidene) ethylidene]-3-methyl-l-(p-sulfophenyl) 2 pyrazolin-S- one, monosulfonated, and the dye bis(l-butyl-3-carboxymethylhexahydro-2,4,6-trioxo-5-pyrimidine) trimethinoxonol, over which is coated light-sensitive silver halide emulsion layer 10.

FIG. 3 shows support 12 coated with antihalation layer 14 comprising gelatin, poly(a-methyl allyl-N-guanidylketimine) the dye 4-[(3-ethyl-2(3H)-benzoxazolylidene) ethylidene]-3-methyl-l-(p-sulfophenyl) 2 pyrazolin-S- one, monosulfonated, the dye bis(l-butyl-3-carboxymethylhexahydro-2,4,6-trioxo-5-pyrimidine) trimethinoxonol and the dye bis[l-(p-sulfophenyl)-3-methyl-2-pyrazolin- 5-one(4)]pentamethinoxono1, over which is coated lightsensitive silver halide emulsion layer 10.

Although the drawing only illustrates the use of our light-filtering layers as antihalation layers between the support and a light-sensitive layer, our light-filtering layers are used advantageously as described previously, such as wherever light-filtering layers are needed in antihalation interlayers between light-sensitive layers, in antihalation backings, in light-filtering layers coated over light-sensit ive layers, etc.

The light filter layers of our invention comprise a waterpermeable hydrophilic colloid, a basic mordant that is a guanylhydrazone derivative such as poly(u-methyl allyl- N-guanidylketimine) and one or more acid substituted benzoxazolepyrazolone merocyanine dyes having both nuclei substituted with an acid group, such that each dye molecule contains two sulfo groups or one sulfo group and one carboxyalkyl group. Our light-filtering'layers also advantageously contain other dyes having two acid groups such as the bis[l-(p-sulfophenyl)-2-pyrazolin-5- one(4)]oxonol dyes, the bis[carboxyalkyl substituted hexahydro-2,4,6-trioxo-S-pyrimidine]oxonol dyes, etc., and certain inorganic pigments which are released from the filter layer upon contact with the normal photographic processing solutions used. The combination of mordant and double' acid substituted dyes used in our light-absorbing layers distinguishes them from light-absorbing layers known before by their unexpectedly good diffusion-fast characteristics and excellent dye releasingproperties. Because of these valuable characteristics our light absorbing layers are particularly valuable for use as antihalation layers between the support and lightsensitive layer or layers. The dyes are so firmly held in the light-absorbing layers that they are coated directly in contact with the silver halide layers without appreciable change in sensitivity of the light-sensitive layers and yet during normal photographic processing, these dyes are released quickly leaving no residual stain.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be eifected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A photographic element comprising a support having coated thereon:

(1) a layer coated from a composition containing a water-permeable hydrophilic colloid, a polymeric mordant having recurring basic groups and a benzoxazole pyrazolone merocyanine dye having on the pyrazolone nucleus a sulfophenyl group, and substituted on the benzene ring of said benzoxazole nucleus an acidic group selected from the class consisting of a sulfo group and a carboxy group, said composition containing said hydrophilic colloid, said polymeric mordant and said merocyanine dye prior to coating on said support, and having coated over said layer,

(2) a layer coated from a light-sensitive silver halide emulsion.

2. A photographic element comprising a support having coated thereon a water-permeable hydrophilic colloid layer from a coating composition comprising a hydrophilic colloid, a vinyl polymer having a recurring structural unit with the formula:

wherein R represents an alkyl group having from 1 to 4 carbon atoms and a dye selected from those having the formula:

wherein R represents an alkyl group having from 1 to 4 carbon atoms; Z represents the nonmetallic atoms necessary to complete a sulfo substituted benzoxazole nucleus having the sulfo group substituted on the benzene moiety of said benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the sulfophenyl-S-pyrazolone series; and n is an integer of from 1 to 3.

3. A photographic element of claim 2 in which the hydrophilic colloid is gelatin.

4. A photographic element of claim 2 in which the dye is 4[(3-ethyl-2(3H) benzoxazolylidene)ethylidene]-3- methyl-l-(p sulfophenyl) 2-pyrazolin-S-one, monosulfonated.

5. A photographic element of claim 2 in which the dye is 4-[4-(3-ethyl-2(3H)-benzoxazolylidene) 2 butenyli- 13 dene]-3-methyl-l-(p-sulfophenyl)-2-pyrazolin one, monosulfonated.

6. A photographic element of claim 2 in which the dye is 4-[4-(3-B-ethyl-2( 3H) benzoxazolylidene)-2-butenylidene] -3-methyl-l-(p sulfophenyl) 2 pyrazolin-S-one, monosulfonated.

7. A photographic element comprising a support having coated thereon a water-permeable hydrophilic colloid layer from a composition comprising gelatin, poly(a methyl allyl-N-guanidylketimine) and the dye 4-[ (3-ethyl- 2( 3H) benzoxazolylidene)ethylidene1-3-methyl l (psulfophenyl)-2-pyrazolin-5-one, monosulfonated and having coated over said hydrophilic layer a light-sensitive silver halide emulsion layer. 1

8. A photographic element comprising a support hav ing coated thereon a water-permeable hydrophilic colloid layer from a composition comprising gelatin, poly (or-methyl allyl-N-guanidylketimine) and the dye 4-[4-(3- ethyl-2(3H) benzoxazolylidene) 2 butenylidene1-3- methyl-l-(p sulfophenyl) 2-pyrazolin-5-one, monosulfonated and having coated over said hydrophilic layer a light-sensitive silver halide emulsion layer.

9. A photographic element comprising a support having coated thereon a gelatin layer coated from a gelatin composition containing (l) poly(a-methyl allyl-N-guanidylketimine); (2) a dye selected from those having the formula:

wherein R represents an alkyl group having from 1 to 4 carbon atoms; Z represents the non-metallic atoms necessary to complete a sulfo-substituted benzoxazole nucleus wherein the sulfo group is substituted on the benzene ring of said benzoxazole nucleus; Q represents the non-metallic atoms necessary to complete a sulfophenyl-S-pyrazolone nucleus; and n is an integer of from 1 to 3; and (3) a dye selected from those having the formula:

/'Q 'Q"\ o=dbH-0H(=0H0H 1=d o=o wherein Q and n are as defined and coated over said gelatin layer, a light-sensitive silver halide emulsion layer.

10. A light-sensitive element comprising a support coated with at least two water-permeable hydrophilic colloid layers such that at least one of said layers comprises a light-sensitive silver halide emulsion and at least one of the other said layers is coated from a composition comprising (1) gelatin, (2) a polymeric mordant having recurring basic groups and (3) a dye selected from those having the formula:

L- R I I o(=oH-cH H=d (3:0

wherein R represents an alkyl group having from 1 to 4 carbon atoms; Z represents the non-metallic atoms necessary to complete a sulfo-substituted benzoxazole nucleus wherein the sulfo group is substituted on the benzene ring of said benzoxazole nucleus; Q represents the non-metal lic atoms necessary to complete a sulfophenyl-S-pyrazolone nucleus; and n is an integer of from 1 to 3.

11. A light-filtering layer coated from a composition comprising a hydrophilic colloid, a vinyl polymer having a recurring structural unit with the formula:

wherein R represents an alkyl group having from 1 to 4 carbon atoms; Z represents the non-metallic atoms necessary to complete a sulfo-substituted benzoxazole nucleus wherein the sulfo group is substituted on the benzene ring of said benzoxazole nucleus; Q represents the non-metallic atoms necessary to complete a sulfophenyl-S-pyrazolone nucleus; and n is an integer of from 1 to 3; and (4) a dye selected from those having the formula:

wherein Q and n are as defined.

13. A light-filtering layer coated from a composition comprising (1) gelatin, (2) poly(a-methyl allyl-N-guanidylketimine), and (3) a dye selected from those having the formula:

wherein R represents an alkyl group having from 1 to 4 carbon atoms; Z represents the non-metallic atoms necessary to complete a sulfo-substituted benzoxazole nucleus wherein the sulfo group is substituted on the benzene ring of said benzoxazole nucleus; Q represents the non-metallic atoms necessary to complete a sulfophenyl-S-pyrazolone nucleus; and n is an integer of from 1 to 3; (4) a dye selected from those having the formula:

wherein Q and n are as defined; and (5) a dye selected from those having the formula:

.waWa o= o=on on=oH).-1=o o-0n wherein W represents the non-metallic atoms necessary to complete a 1-carboxyalkyl-3-hydrocarbon substituted hexahydro-Z,4,6-trioxo-5-pyrimidine nucleus and n is as defined.

14. A light-filtering layer coated from a composition comprising (1) gelatin, (2) poly(u-methyl allyl-N-guanidylketimine), (3) 4-[(3-ethyl-2-(3H) benzoxazolylidene)ethylidene]-3-methyl-l-(p-sulfophenyl) 2 pyrazolin-S-one, monosulfonated.

15. A light-filtering layer coated from a composition comprising (1) gelatin, (2) poly(ot-methyl allyl-N- guanidylketimine), (3) 4-[4-(3-ethyl 2(3H) benzoxazolylidene) -2-butenylidene]-3-methyl-1- (p sulfophenyl) 2-pyrazolin-5-one, monosulfonated.

16. A light-filtering layer coated from a composition comprising (1) gelatin, (2) poly(ot-methyl allyl-N- guanidylketimine), (3) 4-[4-(3-fi-ethyl-2(3H) benzoxazolylidene) -2-butenylidene] -3-methyl-1- (p sulfophenyl) 2-pyrazolin-5-one, monosulfonated.

17. In a multilayer photographic element comprising (a) a support, (b) a red-sensitive silver halide emulsion layer, (c) a green-sensitive silver halide emulsion layer, (d) a blue-sensitive silver halide emulsion layer having substantially no sensitivity in the green and red regions of the spectrum, and (e) a blue-light absorbing colloid layer, said blue-sensitive silver halide emulsion layer (d) being outermost With respect to said silver halide emulsion layers (b) and (c), and said blue-light absorbing layer (e) being beneath said blue-sensitive silver halide emulsion layer ((1) but outermost With respect to said silver halide emulsion layers (b) and (c) the improvement comprising the use of a blue-light absorbing colloid layer (e) coated from a composition comprising:

(1) a hydrophilic colloid;

(2) a polymeric mordant having recurring basic groups; and

(3) a dye selected from those having the formula:

r x r x R11 'I o(=oHoH ,-1= 0:0

wherein R is an alkyl group having from 1 to 4 carbon atoms; Z represents the nonmetallic atoms necessary to complete a benzoxazole nucleus having a sulfo group on the benzene ring of said benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the sulfophenyl-S-pyrazolone series, and n is an integer from References Cited by the Examiner UNITED STATES PATENTS Brooker et a1 9684 Van Dormael et al. 9684 Copeland 9684 Larive 9684 Reed 9684 Minsk 26065 Mader et al 9684 Knott 9610'2 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

20 A. LIBERMAN, R. H. SMITH, Assistant Examiners. 

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING COATED THEREON: (1) A LAYER COATED FROM A COMPOSITION CONTAINING A WATER-PERMEABLE HYDROPHILIC COLLOID, A POLYMERIC MORDANT HAVING RECURRING BASIC GROUPS AND A BENZOXAZOLE PYRAZOLONE MEROCYANINE DYE HAVING ON THE PYRAZOLONE NUCLEUS A SULFOPHENYL GROUP, AND SUBSTITUTED ON THE BENZENE RING OF SAID BENZOXAZOLE NUCLEUS AN ACIDIC GROUP SELECTED FROM THE CLASS CONSISTING OF A SULFO GROUP AND A CARBOXY GROUP, SAID COMPOSITION CONTAINING SAID HYDROPHILIC COLLOID, SAID POLYMERIC MORDANT AND SAD MEROCYANINE DYE PRIOR TO COATING ON SAID SUPPORT, AND HAVING COATED OVER SAID LAYER, (2) A LAYER COATED FROM A LIGHT-SENSITIVE SILVER HALIDE EMULSION. 